Cosmetic compositions containing anionic surface active agent containing mono-or polyhydroxylated mono-or poly ether chains and a terminal acid group

ABSTRACT

A COSMETIC COMPOSITION COMPRISES AN AQUEOUS SOLUTION OF AN ANIONIC SURFACE ACTIVE AGENT HAVING THE FORMULA   R-X-(AO)M-(A&#39;&#39;O)N-A&#34;-X&#39;&#39;-CH(-R&#39;&#39;)-COOH   IN WHICH R IS SELECTED FROM THE GROUP CONSISTING OF ALKYL AND ALKENYL RADICALS HAVING 8 TO 22 CARBON ATOMS AND ALKYL-ARYL RADICALS HAVING 12 TO 22 CARBONS ATOMS; X AND X&#39;&#39; ARE EACH SELECTED FROM THE GROUP CONSISTING OF OXYGEN, SULFUR AND SULFOXIDE; A IS SELECTED FROM THE GROUP CONSISTING OF ETHYLENE, PROPYLENE AND BUTYLENE; A&#39;&#39; IS SELECTED FROM THE GROUP CONSISTING OF   -C2H3(CH2OH)-   AND -CH2CHOH-CH2; A&#34; IX IS SELECTED FROM THE GROUP CONSISTING OF   -CH2CHOH-CH2-,   -CH2CH2CH2-AND-CH2CH(CH3)-, AT LEAST ONE OF THE RADICALS A&#39;&#39; AND A&#34; IS   -CH2CHOH-CH2   OR C2H3(CH2OH); M AND N REPRESENT NUMBERS HAVING A STATISTICAL AVERAGE VALUE BETWEEN 0 AND 10 INCLUSIVE; R&#39;&#39; IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND A LOWER ALKYL RADICAL HAVING FROM 0 TO 2 CARBON ATOMS; AND IN WHICH WHEN M AND N ARE BOTH EQUAL TO ZERO, X&#39;&#39; MUST BE SULFOXIDE.

United States Patent COSMETIC COMPOSITIONS CONTAINING ANIONIC SURFACEACTIVE AGENT CON- TAINING MONO- OR POLYHYDROXYL- ATED MONO- OR POLYETHER CHAINS AND A TERMINAL ACID GROUP Guy Vanlerberghe,Montiay-la-Tour, and Henri Sebag, Paris, France, assignors to SocieteAnonyme dite: LOreal, Paris, France No Drawing. Continuation ofabandoned application Ser. No. 749,580, Aug. 2, 1968. This applicationApr. 24, 1972, Ser. No. 246,864

Int. Cl. A61k 7/00 US. Cl. 424-70 1 6 Claims ABSTRACT OF THE DISCLOSUREA cosmetic composition comprises an aqueous solution of an anionicsurface active agent having the formula V 2 3( 2 and --CH CHOHCH A" isselected from the group consisting of -CH OHOHCH -CH CH CH and -CH CH(CHat least one of the radicals A and A" is or C -H (CH OH); i m and nrepresent numbers having a statistical average value between 0 andinclusive; R is selected from the group consisting of hydrogen and and Iin which when m and n are both equal tozero, X must be sulfoxide. 7

a lower alkyl radical having from 0 to 2 carbon atoms; I

3,822,346 Patented July 2, 1974 at least one of the radicals A and A"being a hydroxyalkylene radical such as --CH CHOH-CH or z 3( 2 m and neach represent a number having a statistical average value between 0 and10 inclusive;

R represents a hydrogen atom or a lower alkyl radical containing 1 or 2carbon atoms; 7

If m and n are both equal to O, X must represent a sulfoxide group.

The present invention also includes the alkaline (Na, K, etc.) andalkaline earth (Mg, Ca, etc.) salts, the ammonium salts, and the aminesalts of carboxylic acids responding to formula I.

It should be noted that one of the essential features of theabove-defined products is that they comprise a monoor polyether chaineither monoor polyhydroxylated between the lipo-philic portion of itsmolecule and the carboxylic acid group. This monoor polyhydroxylatedchain may be preceded by a polyoxyalkylene group. When a single -OHCHOHCH radical is positioned between the lipophilic portion and thecarboxylic group, it is accompanied, as indicated in the abovedefinition, either by a sulfoxide bond or at least one alkylene group.

The properties of the products according to the invention are in generalsimilar to those of the polyoxyalkylenecarboxylic acids heretoforeknown, but they are clearly more accentuated. In particular, thecompounds according to the invention have very valuable properties withrespect to solubility. They dissolve readily in concentrated sodiumhydroxide solutions because they contain the hydroxyalkylene radicalsdesignated by A and A". They also This is a continuation of Applicationser. No. 749,580

filed Aug. 2, 1968, now abandoned.

This invention relates to a new anionic chemical compound which is asurface-active agent and responds to the following formula:

R is an alkyl or alkenyl aliphatic radical having 8to'22 having 12 to 22disperse or dissolve readily in water, and may be used even in hardwater. To be precise, the alkaline earth salts of the carboxylic acidsof this invention will disperse or dissolve in water provided that inthe above general formula, the parameter n has a value equal to orgreater than 0.5 when X is an atom of oxygen or sulfur. Finally theseproducts are readily soluble in an acid medium and highly compatiblewith cationic surface active agents.

' When the compounds of this invention are used in hard water, it shouldbe noted that the above properties are completely unexpected, becausethe most closely similar compounds have no such properties. For example,when any of the known compounds nHzsSCH COONa, c..H,5s-om-co0Na, and

C1nHgs--SCHg-CHz-CO0NB are dissolved in demineralized water at aconcentration of 0.5% turbidity results when an 0.1% solution of calciumchloride is added, whereas then the closely similar compound accordingto the invention:

C Has-0 CH:- CHO H-CHgi-CH: C O O Na,

plete opacity.

The compounds according to the invention have foaming detergentproperties and may be desirably used in shampoos. Their application tothe hair imparts thereto a much softer touch than when alkyl sulfatesare used. The compounds of this invention may also be used as a carrierfor hair dyes which soften the hair.

Any known hair dye can be mixed with the surface active agents of thisinvention to form an improved dye product which colors and softens thehair. Preferred hair dyes to be used in such compositions include nitroamino phenyl hair dyes, quaternary ammonium anthraquinone hair dyes, azohair dyes, etc. Examples 16 to 20 below set forth a few hair dyecompositions containing the hair softening agents of this invention.

Moreover, outside the cosmetic field, the compounds according to theinvention may be utilized for many different purposes, in particular fordegreasing wool, bleaching and mercerizing cotton, etc.

In order to prepare the chemical compounds responding to formula (I) inwhich X represents a thioether bond, a niercapto-alkaneacid or a salt orlow molecular weight ester of such an acid, is reacted witheither: theglycidol ethers responding to the formula:

A'." is identical to A or represents either C H (CH CI) br C H (CH Br ortheallyl alcohol ethers responding to'the formula:

in which R, X, A, A", m and n have the significances hereinbeforeassigned thereto.

When glycidyl ethers responding to formula (II) are used, the esters orsalts of the mercapto-alkanoic acid give the best results. The molarproportion of the mercapto-alkanoic acid, its salts and esters, to theglycidyl ether is of the order of 1 to 1.5 and preferably from 1 to 1.1mols of the former per mol of the latter.

The glycidyl ethers are reacted with the esters or salts of themercapto-alkanoic acids at a temperature between 20 and 150 C. andpreferably between 100 and 120 C. In order to obtain high yields in arelatively short time, alkaline catalysts such as alcoholates,mercaptides, hydroxides and tertiary amines may be used. Among thesuitable tertiary amines are triethylamine, tripropylamine,1,3-N-N-tetramethylbutane diamine and N-N"-tetra-'methylethylene-diamine. When these tertiary amines are used with estersof mercapto-alkanoic acids, thioethers responding to formula (I) areobtained, in theform of methyl or ethyl esters with practicallyquantitative yields. The tertiary amines used as catalysts preferablyconstitute from 1 to 5% of the reaction mixture.

' When the radical A of formula (II) represents a halogenated radicaland when esters of the mercaptoalkanoic acids are used, the resultingthioether-is polyhalogenated, and in order to then obtain the product offormula (I) the halogen atoms must be replaced by a hydroxyl group andthe resulting thio-alkanoic ester must be saponified.

When the parameter n is less than 2, the substitution of the halogenatom by a hydroxyl group and the saponification may be carried outsimultaneously in'a single step by treating the thioether with analkaline reagent such as sodium or potassium hydroxide. These-basesare.used in stoichiometric proportion to the ester andjhalide groups, andby operating at a temperature of about 120 C., a transformation rategreater than 90% is obtainedat the end of about 4 to 5 hours. Thereaction mass issufficiently fluid to render the addition of a solventunnecessary. Moreover, when the medium contains only a smallsubstitution is analogous to the one described in fjrench Pat. No.1,477,048 of April 21, 1966 and the halide formed is separated byfiltration before the saponification.

When the preparation is carried out with allyl ethers respondingto'formula (III), free mercapto-alkanoic acids are preferably used. Theproducts according to formula (I) are then obtained directly at the endof several hours, by simply heating the reaction mixture at atemperature between 25 and 150 C., and preferably between and "C.

The allylethers responding to formula (III) may be obtained: v

7 Either by reacting allyl-glycidyl ether with compounds responding tothe formula RX(AO) H, in which in has a statistical average valuebetween 0 and 10 inclusive and-R, X and A have the significanceshereinbefore'assigned thereto; or by reacting glycidyl ethers respondingto formula(II) withallyl alcohol.

Suitable catalystsfor use in these two reactions include alkalinemetals, alkaline hydroxides, alkaline alcoholates, alkaline mercaptides'and tertiary amines. Acid catalysts, such as boron trifiuoride, stannicchloride, and antimony pentachloride may also be used.

In order to prepare these chemical compounds responding to formula (I)in which X represents sulfoxide group, the corresponding compound inwhich X' represents a thioether group is first prepared, and thenoxidized by adding hydrogen peroxide in the presence of a carboxylicacid, siich for example, as acetic acid. Because'of the difficultyinvolved in the elimination of the said carboxylic acid, it is preferredto use it in a small quantity, for example, about 1 to 2% by weight ascompared to the dry extract of the preparation. This 'oxidation iscarried out at a temperature between 0 and 50 C. and preferably between30 and 35 C.

In order to prepare those chemical compounds according to formula (I) inwhich X represents an oxygen atom, polyetheralcohol alcoholatesresponding to the formula:

RX-(AO) (AO) A"OM (IV) in which R, X, A, A", A'", mand n have thesignificances hereinbefore ascribed thereto and in which M represents analkaline metal, such as sodium, are reacted with a haloalkane carboxylicsalt responding to the formula:

' .Y-CH-COOM' in which I v i R has the significance hereinbeforeindicated, represents an alkaline metal and Y represents a halogen atom,preferably chlorine or bromine.

When in the course of this process, it is desired to -obtain as anintermediate glycerolether'rcsponding to CH CHOHCI-I OI-I h (VI) inwhich R, X, A, m and n have the significances hereinbefore ascribedthereto, and in which Z represents a halogen atom, an alternativeprocess may be adopted by exploiting the reactivity of the acid functionof thehaloalkane carboxylic acids. The above; reaction may thns becarriedout directly .by reacting a haloalkanecar- ""In' order tha inwhich R, A, Z, m and n have the significances hereinbefore indicated andthen treating the resulting product with an alkaline metal hydroxide soas to form in situ the alkaline salt of a haloalkane carboxylic acid andthe alcoholates of the glycerol ethers of formula VI.

,The resulting carboxylic acid polyethe r may be separated from thealkaline salt by using an aqueous solution of a strong mineral acid suchas sulfuric acid, and is thus purified. I

- Finally, the halogen atoms Z are replaced by hydroxyl groups; a 1

In the first step of this process it is preferred to utilize a quantityof haloalkanoic acid mm to 100% in excess of the stoichiometricquantity. Forthe final step, a technique is used which is analogous tothe one described "above for preparing compounds, having thioetherbonds. v 1

7 Compounds of this invention which illustrate the compounds of formulaI and its salts are: p

; ong the alkyl-aryl groups whichmay berepresented by R in form'nlaIare: p-octyl-phenyl p-dodecyl-phenyl ,p-n'onyl-phenyl, I:pj-hexadecyl-phenyl.

resulting"from thefialkylation of phenol with hydro cargbons such, as'diisobutylene, ftri propylene',Itetrapropylene,

.pr hexadece'ne..,

f the inventioh 'm'ay be better understood, several methodsof preparingcompounds.accordmg to formula (I) and .severalexamples showmg how these6 compounds may be used in the cosmetic field will now be described:

EXAMPLE 1 Preparation of the compound responding to the formula:

3.5 ml. of triethylamine is added to 120 g. (1 mole) of ethylethioglycolate under a nitrogen atmosphere. The mixture is brought to100 C. and 242 g. (1 mole) of distilled dodecyl-glycdyl ether is addeddrop by drop. Heating is continued for about three hours. The reactionis then practically complete. The excess ethyl thioglycolate is theneliminated under vacuum.

The ester thus obtained is then poured into 200 cc. of acetic acid and 1mole of hydrogen peroxide at 130 volumes (50% diluted with acetic acid)is then added drop by drop. The reaction is exothermic and thetemperature is kept between and C.

After resting overnight at room temperature, no more free peroxidesremain. The mixture is then heated under vacuum to eliminate the aceticacid. On cooling the sulfoxide crystallizes out.

The product is redissolved in 200 to 250 cc. of CH OH and 100 g. of NaOHand the sodium soap is precipitate'd' with acetone. The result is anordorless white powder.

EXAMPLE 2 I Preparation of the compound responding to the formula:

R-oonno onionun-cm-cnon-onz-s-cmc OONa up to .190? C. follows.

7 in which R represents an aliphatic radical containing 12 to 14 carbonatoms and n has a statistical average value of 0.5.

1.6 ml. of a boron fluoride acetic acid. complex is added to 396 g. (2moles) of a mixture of fatty alcohols consisting essentially ofdodecanol and tetradecanol. 277 g. of epichlorohydrin is then added dropby drop, at 75 to 80 C. When the reaction is complete the product ispoured into 675 g. of tertiobutyl alcohol and 300 g. of 40% NaOH'isadded. This is heated for an hour at 75 C. After adding the quantity ofwater required to dissolve the salt thus formed, salting out yields theepoxide in tertiobutyl alcohol. 1

300 g. 1 mole) of the epoxide obtained by distilling the tertiobutylalcohol is added, drop by drop, at 105 to 115 C, under a'nitrogenatmosphere, to 132 g. (1.1 moles) of ethyl thioglycolate and 4.5 cc. oftriethylamine. This temperature is maintained for 3 hours. The reactionis then complete. The excess ethyl thioglycolate is then eliminated byheating under a vacuum.

The remaining chlorinated compound is hydrolized in a reactor providedwith powerful agitating means. 150 g.

(1.5 moles) of 40% NaOH is added to 420 g. (I1 mole) 7 of the resultingester. The liberated alcohol, plus part of the water introduced, isdistilled until a temperature of 120 to 125 C. is attained. Thistemperature is maintained for 4 hours and a half. The percentage ofhydrolysis is" The resulting product is a white cream containing about50% of the active components.

EXAMPLE 3 Preparation of the compound responding to the formula:

8 1 Preparation of the compound responding .10.; the

formulaz p 1 iz zs o-r Hz 'l fa-fof" The reaction consists-in addingthioglycolic a'cidto allyl ether and 2-hydroxy-3-lauryloxy propyl. Thelatter compound is prepared by condensing" lauric alcohol onallyl-glycidyl ether in the presence of sodium methylate in.theiiollowing'manner: r- 1 t q t 1 15 "g. ofallyl-glycidylaethenis.added, drop by. drop, in 20. minutes to 186 g. oflauric alcohol and1.2 g.;of.sodium methylate,whichhavebeen heated to 12010 14 0? ,C. The mixture is ,then heatedto;160 C. for 4 hours.Distillation of the crude product obtained in this manner separates theallyl ether and the Z-hydroxy-S-lauryloxy.propyll This is distilled at\150 to 170C. under a pressure of 1 mm. of mercury. g. (0.2 mole) ofethylene derivative and 10 g. (0.2 mole) of thioglycolic acid are mixedand heated to 100 C. for 8 or 9 hours. About of the mixture reacts, H p

The acid "index indicates that the product is partially esterified. Itis first neutralized and then saponified with a stoichiometric quantityof 40% NaOH in the presence of alcohol. After distillation of thealcohol, the yield is an almost colorless wax, which is soluble inwater.

EXAMPLE 5 Preparation of the compound responding to the formula:

I As in Example 4, the product is prepared by adding thioglycolic acidto the corresponding ethylene derivative. This ethylene derivative isprepared by adding lauryl mercaptan, drop by drop, at to C. to an excess(200%) of allyl-glycidyl ether while bubbling in nitrogen,andinthepresence' of 'triethylamine, which constitutes 0.5% of thereaction mass. This addition takes thirty minutes. The reaction:is.almost instantaneous.

in which R represents an oleyl radical and n has a statistical averagevalue of 3.

An epoxide is prepared from the compound obtained by reacting 4 moles ofepichlorohydrin and oleic alcohol, 1

according to the method indicated in Example 2. 240 g.

of the epoxide produced in this manner is added drop bydrop to 53 g. ofethyl thioglycolate and 2 cc. .of triethyl-' added in 30 minutes, undera nitrogen atmosphere, at C., to 115 g. of potassium acetate in 285 g.of diprop'ylene" glycol. Heating is continued for four hours. Theresulting salt is filtered at "100 C. and rinsed with dipropyleneglycol. Distillation under -a pressure of 15 mm. of mercury The residueis redissolved in 250 cc. of absolute alcohol and 750 mg. of CH ONa.After leaving it overnight at room temperature, the resulting ethylacetate andalcohol are distilled, ending up under vacuum at 1 80 C, m5

The product is again dissolved in a little alcoholand the ester issaponified with a stoichiometric quantity.o 40

sodium hydroxide. Distillation of the alcohol leavesi a Thecorresponding magnesium salt obtained by double decomposition betweenthe sodium salt and magnesium chloride in an alcoholic medium isperfectly soluble in water.

can? engcaoa enao w. I

The excess allyl-glycidyl-ether is eliminated. Then the desired ethylenederivatiye is distilled at C. under 0.5 mm. of mercury. Astoic'hiometric quantity (7.2 g.) of thioglycolic acid is added drop bydrop, to 28 g. of

the resulting.compound..;After this addition, the mixture is heatedjorfive minutes at 100 C. The acid which has not reacted'is eliminatedunder vacuum. On cooling," the condensation product crystallizes. Thisis then rinsed in petroleum ether and an attractive white powderresults.

The sodium soap is obtained by neutralizing this powder with 50% sodiumhydroxide in an alcoholic medium and precipitation with acetone.

EXAMPLE 6 Preparation of the compound responding to the formula:

50% NaOH in alcohol and pre pitation causedaddlrig 'pewder' whicli'dis'solvesr'eadily inwater.

' the torm of "white 9 EXAMPLE 7 Preparation of the compound respondingto the formula:

in which R represents an aliphatic radical containing 12 k} g45carbonatoms and n has a statistical average value 400 g. (1.33 moles) ofepoxide prepared as in Example 2 is added over thirty minutes at 120 C.to 151 g. of monochloroacetic acid in the presence of 11 cc. oftriethylamine. It is then heated for three hours at 150 C. After coolingto60 .C., 127.5 g. of sodium hydroxide flakes is added. The reaction isexothermic. This temperature is maintained until all the sodiumhydroxide has reacted- 84' g. of sodium hydroxide flakes and 101 g. ofmonochloroacetic acid are each divided into three parts and addedalternately.

The mixture is introduced into 1500 cc. of water and 400 g. of sulfuricacid at half-normal strength is added. On heating to 100 C. the acidsalts out. 528 g. of the re- This is heated for 6 hours at between 120and 160 C. 42 g. of sodium hydroxide flakes are added at a temperatureof 60 C. and heated hours at 60 to 80 C. 76 g. of sodium hydroxideflakes and 89 g. of monochloroacetic acid are each divided into threefractions and added alternately to the mixture.

This is then acidified with 41.5 cc. of sulfuric acid, while adding 800c. of water and heating and stirring for an hour in a water-bath. Thecarboxylic acid salts'out perfectly, and is separated and vacuum dried.

The corresponding sodium salt is prepared by adding to this salt in analcoholic medium as much 40% sodium hydroxide as is necessary to salifythe carboxylic function and hydrolize the remaining chlorine. Themixture is then heated at reflux for 10 minutes, the alcohol distilledoff, and the mixture heated to 125 C. for four and a half hours, as inExample 2.

EXAMPLE 9 Preparation of the compound responding to sulting acid isredissolved in 150 g. of alcohol at 96 C. and sufiicient 40% sodiumhydroxide aqueous solution is added to neutralize and hydrolize theorganic chlorine.

The alcohol and part of the water is distilled off until a temperatureof 120 C. is reached. This temperature is maintained for 4 hours and thehydrolysis is 96% complete.

On cooling, the yield is a hard product, which can be molded, but is alittle fragile.

. EXAMPLE 8 Preparation of the compound responding to the formula:

. 0tc2 3 H3) 1mrcH3 (c 2 Hi1n- CH -CH-CH This epoxide is prepared in thefollowing manner.

6.25 of a boron fluoride acetic acid complex is added to one mole ofmolten stearylalcohol which has been dehydrated by heating under a mm.pressure in a boiling water bath, and 5 .25 moles of propylene oxide isthen added drop by drop. The reaction is exothermic and takes place at75 to 80 C. The addition of the propylene oxide takes from 1 hour andminutes to 1 hour and 45 minutes. a

' Theepichlorhydrin is condensed immediately after oxypropylenation, at75 to 80 C. over a period of 30 minutes. The resulting polychlorinatedpolyether has a hydroxyl index of 90. H W W An equal weight oftertiobutyl alcohol is added to this polychlorniated polyether and inten minutes, 150 g. of.

40% sodium hydroxide is also added, and the mixture heated to for 30minutes. The minimum amount of Water required to solubilize theresulting salt, and the aqueous phase separated by decantation. .Theorganic phase is dried on sodium suflate, and filtered. The tertiobutylalcohol is distilled olf. The yield is an epoxide which titrationindicates to comprise 1.62 m.e.g./g. of oxirane groupspg... 3' v inwhich R, m and n have the same significances as in the precedingexample.

This is prepared from the sodium salt obtained as set forth above. 0.2mole of this salt is dissolved in 50 cc. of water and 50 cc. of alcohol.At 60, 40 gr. of MgCl (100% excess), dissolved in 100 cc. of water, isadded. The mixture is heated at 70 C. for an hour and a half and thenpoured into 700 to 800 cc. of water which has first been heated to C.

This aqueous phase is drawn 0E, and drying yields the magnesium salt,which takes the form of a brown paste. The percentage of magnesium inthe product and in the mother liquor is about 80%. This product may beused as an emulsifier. I

EXAMPLE 10 The following compositions was prepared:

. Grams 011E150 CHz-CHOH-CHz-S-CHrCOONB 10 Lain-1c dipfhnnnlamifln 2Soybea lenirhin 0. 5 2-butoxy ethanol 0. 5 Hydroxypropylmethylcellulose0. 2 Water, q.s.p

The pH of the composition is at least equal to 7. It is limpid, hasvaluable foaming properties, and may be used in a' quantity of about 20cc. as a shampoo for the hair.

EXAMPLE 11 The composition has a pH of 7, is limpid, and has valuablefoaming properties. It may be used, in a quantity of about 20 cc., as ashampoo for the hair.

Water, q.s.p. 100 g. ""The composition has a pH of 7, is limpid, and hasvaluable foaming properties. About 20 cc. serves as an excellent shampoofor thehair. I

' EXAMPLE 13 The following composition was prepared:

G. C H OCH CHOHCH OCH -(C H )S- 'CH' COONa- L 6 Sodium salt of sulfuricester of lauryl alcohol poly-- ethoxylated with two moles of ethyleneoxide 5 Lauryl diethanolamide 2.5 Acetylated lanolin 0.5

Water, q.s.p. 100 g.

The composition has a pH equal to 7, is'limpid, and has valuable foamingproperties. 20 cc. makes an excellent shampoo for the-hair.

EXAMPLE 14 The following composition was prepared:

G. R-[OzH3O (CHzOH)]nCHnOHOH-CHz-O CH 0 ONa -In this formula Rrepresents an alkyl radical containing 12 to 14 carbon atoms and n has astatistical average value of 0.5. -Acetylated lanolin 1Hydroxypropylmethylcellulose 0.25.

Sodium salt of sulfuric ester of lauryl alcohol polyl ,ethoxylated with2 moles of ethylene oxide 5 Lauryl diethanolamine l.. ,2Hydroxypropylmethylcellulose 0.2

Water, q.s.p. 100 g.

The composition hasa pH of 7, is'limpid, and has valuable-foamingproperties. ccserves as anexcellent hamanic: the. air.

contained about 2.2 molecules of 2 EXAMPLE 16 I The following dyeingcomposition was prepared:

Grams B is-methyl[1,5 ('y-trimethyl-ammonium) propylaminoanthraqninone]sulfate 1.

C12H25QCH2CHOHOHz-?CH2COONB 2. 00

20% solution of isooctylphenylpolyethox yethanol. 4. 60Monoethanolamine, q.s.p., pH 8 Water, q.s.p

In order to do this, 1.65 g. of bis-methyl-[LSOy-trimethylammonium)propylaminoanthraquinone] sulfate is dissolved in the minimum possibleamount of water and adjusted to pH 7 with monoethanolamine. Into thissolution 100 g./liters of a solution of is poured drop by drop from aburette. Beginning with the first drop, a deep red product begins toprecipitate. The course of this precipitation is tested by drops onfilter paper and it was found that the precipitation increases inproportion to the quantity of the product responding to .the aboveformula introduced, while the solution clears. The maximum precipitationoccurs when 20 cc. of the surface active solution was used. The solutionbecomes color less. A slight excess of the product according to theabove formula produces a tendency to redissolve the precipitate. Theresulting product was dissolved in the minimum quantity of a 20%solution of isooctylphenylpolyethoxyethanol. The course of thisredissolution was followed by depositing drops of the solution on filterpaper using a burette. It required 23 cc. of a 20%isooctylphenylpolyethoxyethanol solution to completely redissolve thisproduct. The pH was adjusted to 8 with monoethanolamine, the solutionwas increased to 100 g., and no reprecipitation was noted. It was foundthat this product the product responding to the formula:

for each molecule of dye. (This is very close to a stoichiometric.proportion, since bis-methyl[1,5('y-trimethyl-ammonium)propylaminoanthraquinone]sulfate is dibasic.)

This composition was applied to chestnut hair. The

- product was a good foam former. It is left on the hair for v 15minutes. The hair is then washed and rinsed. A strong mahogany shaderesults.

EXAMPLE 17 Grams"BlS-mothy1[1,5('y-trimethyl-ammonium)-propylaminoanthraquinone]suli'ate1.65 R-[oozngonomkoCnoHorgcms-cmcoom aao (in which formula R representsan aliphatic radical containing 12 to 14 carbon atoms and n=0.5.)

20'? solution oiisooc l hen l 01 ethox ethanol 4.30 -Moiioethanolamine,- 5231,31 y y i 8 Water, q.s.n 100 The followingcomposition was prepared:

14 X and X are each selected from the group consisting of oxygen, sulfurand sulfoxide; A is selected from the group consisting of ethylene,propylene and butylene; A is selected from the group consisting of and4-N-methylamino-3-nltro-N-;8-aminoethylamino benzene .fiuIi representsoleyl and 11:1 isooetylphenylpolyethoxyethanol solutiom-Monoethanolamine, q.s.p., pH Water, q.s.p

EXAMPLE 19 The following composition was prepared:

Grams 4-N-methylamino-3-nitro-1-N-B-aminoethylarnino benzene 0. 29lR-[OCzH3(CH2OH)}nOOHr-CHOH-OHr- 2- COONa (in which formula R is oelyland n=1 0. 53 20% isooetylphenylpolyethosyethanol solution 1. 60 lllonoethauolamine, q.s.p., pH 8 Water, q.s.p 100 In preparing the activeproduct it is difiicult to detect any precipitation since this productis very soluble. A stoichiometric quantity of anion was therefore used.

When applied as in Example 18 this composition also produces a Violineshade, but one a little less red than in the preceding example.

EXAMPLE 20 The following composition was prepared following the sameprocedure as in Example 16:

Grams Bis-methyl[1,5-('y-trimethylammonium)-propylaminoanthraquinone]sulfatn 1. 65 R-[O Ca a(CH2OH) ..O CHrCHOHCHzSCHi- OOONe (in whichrepresents an aliphatic radical containing from 12 to 14 carbon atomsand n=0.5) 2. 6 20% isooctylphenylpolyethoxyethanol solution 3. 20Monoethano1amlne,q.s.p,pH 8 Water, q s p 100 In this case the anion isin 20% excess of stoichiometric proportions. The composition is veryfoam-forming.

It was applied to chestnut hair and left thereon for fifteen minutes,after which the hair was rinsed and shampooed. The result was a verystrong mahogany color.

What is claimed is:

1. A cosmetic composition comprising in an aqueous solution asurface-active agent having the formula wherein R is selected from thegroup consisting of alkyl and alkenyl, each having 8-22 carbon atoms andalkyl phenyl selected from the group consisting of p-octyl phenyl,p-nonyl phenyl, p-dodecyl phenyl and p-hexadecyl phenyl;

A" is selected from the group consisting of CH CHOH'CH -CH CH CH and -CHCH(CH3), with the proviso that at least one of A and A" ishydroxyalkylene as set forth in the respective definitions of A' and A"above;

m and n represent numbers having a statistical average value between0'10 inclusive, with the proviso that n is other than 0 when A" is otherthan hydroxyalkylene and when m and n are both equal to zero, X issulfoxide; and

R is selected from the group consisting of hydrogen and alkyl havingfrom 1-12 carbon atoms,

said surface active agent being present in amounts ranging from 01-20%by weight of said composition.

2. The composition of claim 1 having a pH of 3-10. 3. The composition ofclaim 2 for use as a hair shampoo and having a pH of 7.

4. The composition of claim 3 wherein said surface active agent has theformula CnHzgO-CHzCHOH-CHz-S CH:C O ONa.

5. The composition of claim 3 wherein said surface active agent has theformula 6. The composition of claim 3 wherein said surface active agenthas the formula wherein R is alkyl containing 12-14 carbon atoms and nhas a statistical average value of 0.5.

References Cited UNITED STATES PATENTS 3,427,248 2/ 19 69 Lamberti eta1. 252117 2,111,820 3/1938 Steindorff et al. 252-356 X 2,183,85312/1939 Hausmann et al. 260- 535 X 2,623,900 12/ 1952 Hofer 260 -535 X2,745,857 5/ 1956 Britton et al 260--535 X ALBERT T. MEYERS, PrimaryExaminer N. A. DREZIN, Assistant Examiner US. Cl. X.R.

8l0.l; 252356; 260- 535 R; 424-317, 365

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 822 I 4Dated July 2 1974 Inventor(s) Guy Vanlerberghe and Henri Sebaq 7 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In the Heading: 7

Please add the following:

Claims priority, application Luxembourg August 7, 1967, 54,263

Signed and sealed this 19th day of November 1974.

(SEAL) Attest:

Y MCCOY M. GIBSON JR. C. MARSHALL DANN Attesting' Officer Commissionerof Patents USCOMM-DC 60376-P69 FORM Po-wso (10-69) I v v U S.GOVIINIEII' PRIN'INO O'IICE Iil O-366 -!3l UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION PatentNo. 3,822,346 Dated u y y 14 Inventofls)Guy Vanlerberghe and Henri Sebaq It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

In the Heading:

Please add the following:

Claims priority, application Luxembourg August 7, 1967, 54,263

Signed and sealed this 19th day of November 1974.

(SEAL) Attest:

a McCOY M. GIBSON JR. c. MARSHALL DANN Attesting Officer Commissioner ofPatents FORM po-aoso (10-69) USCOMWDC 0037M, Y Q U 5. GOVIRNIIUY PRN'ING OFFICE "II 0-866

